CN112993253A - High-performance silicon-based lithium ion battery cathode material and preparation method thereof - Google Patents
High-performance silicon-based lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN112993253A CN112993253A CN202110055605.0A CN202110055605A CN112993253A CN 112993253 A CN112993253 A CN 112993253A CN 202110055605 A CN202110055605 A CN 202110055605A CN 112993253 A CN112993253 A CN 112993253A
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Abstract
The invention discloses a high-performance silicon-based lithium ion battery cathode material and a preparation method thereof, belonging to the technical field of battery material preparation. The cathode material is of a core-shell structure, the inner core is silicon-based particles/M-carbon composite particles, M is transition metal or a compound thereof, and the coating layer is a carbon layer; the preparation method comprises the following steps: firstly, preparing a silicon-based particle/M composite material as a first precursor material; adding a carbon source material, uniformly mixing with the first precursor material, and performing secondary granulation to obtain silicon-based particles/M-carbon particles as a second precursor material; and finally, coating a uniform and continuous carbon layer on the surface of the second precursor material in a solid-phase sintering or vapor deposition mode. The invention activates the inert product generated in the process of lithium intercalation of the silicon-based material by introducing the substance containing the transition metal element, thereby improving the first coulomb efficiency of the silicon-based material. Meanwhile, the process can realize the industrial production of the lithium ion battery with excellent performances such as high specific capacity, long cycle life and the like.
Description
Technical Field
The invention belongs to the technical field of battery material preparation, and particularly relates to a silicon-based lithium ion battery cathode material and a preparation method thereof.
Background
In the lithium ion battery cathode material, silicon not only has high theoretical specific capacity (4200mAh/g) and a reasonable lithium intercalation/deintercalation potential platform, but also has rich sources, low price and environmental friendliness, and is considered to be a new generation of lithium ion battery cathode material which is expected to replace graphite.
However, silicon negative electrodes are often accompanied by large volume expansion (up to 300%) during lithium extraction/insertion, and their own conductivity is not high, which easily causes particle crushing and pulverization, thereby inactivating the material. In addition, a silicon surface Solid Electrolyte Interface (SEI) film is also continuously broken and proliferated, resulting in severe attenuation of cycle performance, and finally causing a battery to have large first irreversible capacity and poor rate capability.
The research and development of the existing silicon-based electrode material of the lithium ion battery are focused on the aspects of high capacity, high rate performance, high cycle stability and long service life, and the attention to the initial coulombic efficiency is less. For example, chinese patent application CN110391406A discloses a lithium ion battery silicon-oxygen cathode material with high rate performance, which is prepared by first obtaining graphite powder doped with elements through high-speed ball milling, and further adding silicon oxide and coating a layer of pyrolytic carbon to finally obtain a silicon-oxygen cathode with a core-shell structure. The chinese patent application CN110021737A utilizes transition metal elements to catalyze graphitization of organic carbon source, and improves the cycling stability of the cell corresponding to silicon carbon material.
Silicon protoxide (SiO)x) The material has the most practical prospect in the silicon-based material, and can generate an inert component in situ in the lithium removal/insertion process, thereby properly relieving or solving the problem of poor cycle performance of the silicon-based material. But SiOxFormation of Li during the first intercalation of lithium2The irreversible reaction of O and lithium silicate consumes active lithium ions to form 'dead lithium', so that the initial coulomb efficiency of the battery is greatly reduced, generally only 50-80%, and thus, the silicon monoxide has serious defects in the aspect of the initial coulomb efficiency, and the integral energy density of the battery is reduced. In addition, the consumption of the positive electrode material undoubtedly further increases the battery cost.
Pre-lithiation (Journal of Power Sources 195(2010) 6143-. However, lithium metal powders are generally highly reactive and require special handling during raw material storage and transportation, thereby increasing battery cost. And the metal lithium powder generally has larger particles, is difficult to realize uniform dispersion in the electrode, and easily causes the aggregation and growth of lithium in the lithium intercalation process due to excessive addition, generates lithium dendrite and generates potential safety hazard.
The introduction of metal or metal compound into the silicon-based material is an important means for improving the electrochemical performance of the silicon-based material, but the common metal and the silicon in the silicon-based composite material are difficult to form good bonding, so that the nano metal and Li are difficult to pass through2O orThe reversible conversion of lithium silicate achieves the aim of improving the first coulomb efficiency of the silicon-based material. The metals and metal compounds usually introduced only increase the electrical conductivity of the material, stabilize the material structure, and reduce the volume expansion of the composite material. Therefore, the method effectively improves the capacity, multiplying power and cycling stability of lithium ions by a compounding strategy of the silicon-based material and the metal or metal compound, improves the initial coulomb efficiency, is always a difficult point for researching the negative electrode material of the silicon-based lithium ion battery, and has important significance.
Disclosure of Invention
Aiming at the problem that the first coulombic efficiency is low when a silicon-based material is used as a lithium ion battery cathode material, the invention provides a high-performance silicon-based lithium ion battery cathode material and a preparation method thereof. The process can realize the industrial production of the lithium ion battery with excellent performances such as high specific capacity, long cycle life and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a high-performance silicon-based lithium ion battery cathode material, which is of a core-shell structure, wherein a core is silicon-based particles/M-carbon composite particles, M is transition metal or a compound thereof, and a coating layer is a carbon layer; the inner core is prepared by a method of firstly obtaining silicon-based particles/M composite material by silicon-based particles and a transition metal source, and then adding a carbon source for secondary granulation.
Further, the mass percentages of the elements in the negative electrode material are as follows: si: 5-99 wt%; o: 0 to 55 wt%; c: 0.5-90 wt%; n: 0-15 wt%, S: 0-15 wt%, P: 0 to 15 wt%, transition metal: 0.01-30 wt%.
Further, the transition metal element in M comprises one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Cu, Ag, Au and Pt; the existence form of M in the silicon-based particles/M-carbon composite particles comprises one or more of simple metal, metal-carbon alloy, metal-silicon alloy, metal nitride, metal oxide, metal phosphide, metal sulfide and metal silicate.
The invention also provides a preparation method of the high-performance silicon-based lithium ion battery cathode material, which comprises the following steps:
(1) preparing a silicon-based particle/M composite material as a first precursor material by taking silicon-based particles and a transition metal source as raw materials;
(2) adding a carbon source material, uniformly mixing with the first precursor material, and obtaining silicon-based particles/M-carbon particles as a second precursor material by a secondary granulation method;
(3) and coating a uniform and continuous carbon layer on the surface of the second precursor material in a solid-phase sintering or vapor deposition mode to finally obtain the silicon-based particle/M-carbon @ carbon composite material.
Further, the silicon-based particles in step (1) comprise one or more of elemental silicon, a silicon-carbon composite material, a silicon oxide and a silicon oxide/carbon composite material.
Further, the average particle diameter of the first precursor material in the step (1) is 0.005-1 μm, and the specific surface area is 0.5-1000m2/g。
Further, the preparation method of the first precursor material in the step (1) is selected from any one of a vapor deposition method, a wet chemical method, a physical mixing method and a solid-phase sintering method.
Furthermore, the vapor deposition method includes chemical vapor deposition and physical vapor deposition.
The vapor deposition method in the invention means that a transition metal source is gasified at a proper temperature, introduced into a reactor and deposited on a solid phase silicon-based material at a specific temperature and in a specific atmosphere to obtain a first precursor material.
Wherein the temperature of vaporization or sublimation of the transition metal source is 50-800 ℃.
The transition metal source comprises one or more of metal organic complexes, metal inorganic complexes and inorganic metal compounds which are combined in any proportion; the metal organic complex comprises carbonyl metal, aryl metal, cyclopentadienyl metal or alkyl metal; the inorganic metal compound includes a metal halide.
The reaction temperature of the vapor deposition is 120-1300 ℃, and the deposition reaction time is not less than 0.1 h; the temperature rising/reducing rate is controlled to be 1-100 ℃/min, and the temperature rising/reducing rate is changed along with the reaction process.
The air pressure in the vapor deposition reactor is 0.1-200 kPa; the filling gas and the purging carrier gas are one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton, xenon, ammonia, hydrogen sulfide, phosphine and water vapor; the gas flow rate is controlled in the range of 1-1000 sccm.
The reactor comprises a fixed bed, a moving bed or a fluidized bed.
Furthermore, the wet chemical method comprises a precipitation method, a sol-gel method, alkoxide hydrolysis, a hydrothermal method, a microemulsion method, an electrolysis method, mixing and evaporating to dryness and the like.
The wet chemical process of the present invention comprises the steps of:
(1-1a) dispersing a transition metal source in a solvent, adding a certain amount of an additive, and fully mixing;
(1-1b) adding silicon-based particles into the mixed solution according to a certain proportion, and fully mixing;
(1-1c) carrying out precipitation, hydrolytic condensation, hydrothermal treatment, agglomeration by coalescence, evaporation to dryness or electrodeposition treatment for 0.5-100h at the temperature of 0-300 ℃ to obtain a silicon-based material precursor uniformly combined with M;
(1-1d) sequentially carrying out centrifugal separation, drying, heat treatment and crushing on the precursor to obtain a first precursor material.
Wherein, the transition metal source in the step (1-1a) is one or more of inorganic compounds or organic compounds containing transition metals in any proportion.
In the step (1-1a), the solvent comprises one or more of water, sulfuric acid, liquid ammonia, carbon disulfide, hydrocarbons, hydrocarbon derivatives, alcohols, ethers, ketones, carboxylic acids, glycol derivatives, nitriles, amines, pyridine, phenol and acetone in any proportion.
The additive in the step (1-1a) comprises one or a combination of several of pH regulating agent, surfactant and precipitator; the pH adjusting reagent comprises ammonia water, sodium hydroxide, nitric acid or hydrochloric acid; the surfactant comprises polyacrylic acid, hexadecyl trimethyl ammonium bromide, polyvinylpyrrolidone, alkyl sulfonate, quaternary ammonium salt, fatty acid salt, lecithin, amino acid type, betaine type, polyalcohol or polyoxyethylene type surfactant; the precipitant comprises carbonate, strong base, ammonia water, urea or acetic acid.
And (3) adding the pH regulating reagent into the solution to regulate the pH value to be within the range of 3-11 in the step (1-1 a).
The mass ratio of the metal source to the surfactant or the precipitating agent in the step (1-1a) is 0.01-100; the ratio of the addition amount of more than two surfactants or precipitants is between 0.01 and 100.
The mass ratio of the transition metal source to the added amount of the silicon-based particles in the step (1-1b) is 0.005-1000.
The rotation speed of the centrifugal separation in the step (1-1d) is 500-10000r/min, and the time is 0.5-1000 min.
The drying in the step (1-1d) comprises ordinary drying, forced air drying, vacuum drying or freeze drying, the drying time is 0.5-50h, and the drying temperature is 30-250 ℃ except for freeze drying.
The temperature of the heat treatment in the step (1-1d) is 200-; the heat treatment atmosphere comprises normal pressure/low pressure purging and ventilating and pipe sealing closed atmosphere, the purging gas comprises one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton, xenon, ammonia, hydrogen sulfide, phosphine and water vapor in any proportion, and the gas flow is 1-1000 sccm.
Still further, the physical mixing methods include mechanochemical and high energy ball milling methods.
The physical mixing method comprises the following steps:
(1-2a) mixing a transition metal source, silicon-based particles and an additive, and performing mechanical crushing, mechanical pressure, ultrasonic treatment or ball milling treatment to obtain a condensed transition metal-containing silicon-based material precursor;
(1-2b) sequentially carrying out centrifugal separation, drying, heat treatment and crushing on the precursor to obtain a first precursor material.
Wherein the transition metal source in step (1-2a) comprises transition metal-containing inorganic salts, organic salts, nitrides, oxides, sulfides, phosphides, halides; the mass ratio of the transition metal source to the added amount of the silicon-based particles is 0.005-1000.
The additive in the step (1-2a) comprises one or two of a pH adjusting agent and a surfactant; the pH adjusting reagent comprises ammonia water, sodium hydroxide, nitric acid and hydrochloric acid; the surfactant comprises polyacrylic acid, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, alkyl sulfonate, quaternary ammonium salt, fatty acid salt, lecithin, amino acid type, betaine type, polyalcohol and polyoxyethylene type surfactant.
In the step (1-2a), the pH value of the pH regulating reagent is regulated to be within the range of 3-11 by adding the solution.
In the step (1-2a), the mass ratio of the metal source to the surfactant is 0.01-100, and the adding amount ratio of more than two surfactants is 0.01-100.
In the step (1-2a), the ball milling rotation speed is 50-1000r/min, the time is 0.5-100h, and the ball milling temperature is controlled at 1-200 ℃; ball milling is carried out in a vacuum low-pressure state or reaction gas is introduced into a ball milling tank for ball milling; the reaction gas comprises one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton, xenon, ammonia, hydrogen sulfide and phosphine.
When wet milling is adopted in the step (1-2a), the added solvent comprises one or more of water, sulfuric acid, liquid ammonia, carbon disulfide, hydrocarbons, hydrocarbon derivatives, alcohols, ethers, ketones, carboxylic acids, glycol derivatives, nitriles, amines, pyridine, phenol and acetone in any proportion.
The drying in the step (1-2b) comprises ordinary drying, forced air drying, vacuum drying or freeze drying, the drying time is 0.5-50h, and the drying temperature is 30-250 ℃ except for freeze drying.
The temperature of the heat treatment in the step (1-2b) is 200-; the heat treatment atmosphere is normal pressure/low pressure purging and ventilating and pipe sealing closed atmosphere, wherein the purging gas comprises one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton, xenon, ammonia, hydrogen sulfide, phosphine and water vapor in any proportion, and the gas flow is 1-1000 sccm.
Further, the solid-phase sintering method includes a thermal decomposition method, a thermal reduction method, a high-temperature solid-phase reaction method.
The solid-phase sintering method comprises the following steps:
(1-3a) mixing a transition metal source, silicon-based particles and a surfactant, and performing ball milling, sanding or stirring to obtain a solid mixture;
(1-3b) sequentially carrying out high-temperature treatment and crushing on the mixture to obtain a first precursor material.
Wherein the mass ratio of the transition metal source to the added amount of the silicon-based particles in the step (1-3a) is 0.005-1000.
The surfactant in the step (1-3a) includes polyacrylic acid, cetyltrimethylammonium bromide, polyvinylpyrrolidone, alkylsulfonate, quaternary ammonium salt, fatty acid salt, lecithin, amino acid type, betaine type, polyhydric alcohol, polyoxyethylene type surfactant.
The mass ratio of the metal source to the surfactant in the step (1-3a) is 0.01-100.
In the step (1-3a), the rotation speed of ball milling or sanding is 50-1000r/min, the time is 0.5-100h, and the ball milling temperature is controlled at 1-200 ℃; grinding in a vacuum low-pressure state or introducing reaction gas into a grinding tank for ball milling; the reaction gas comprises one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton, xenon, ammonia, hydrogen sulfide and phosphine.
The temperature of the high-temperature treatment in the step (1-3b) is 200-; the high-temperature treatment atmosphere is a normal pressure/low pressure purging and ventilating and pipe sealing closed atmosphere, wherein the purging gas comprises one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton, xenon, ammonia, hydrogen sulfide, phosphine and water vapor in any proportion, and the gas flow is 1-1000 sccm.
Further, the carbon source material in the step (2) comprises one or more of saccharides, resins, rubbers, asphalt, polyvinylpyrrolidone, organic acids, polyethylene and derivatives thereof, polyalcohols, polyvinyl alcohol and derivatives thereof, or solid-phase carbon source materials in any ratio; the solid-phase carbon source material comprises carbon fiber, graphite, graphene, carbon black, carbon nanoparticles, onion carbon, activated carbon or carbon nanotubes; the average grain diameter of the solid-phase carbon source material is 0.005-150 mu m, and the specific surface area is 0.05-1000m2/g。
Further, the mass ratio of the first precursor material to the carbon source material in the step (2) is 0.01-100.
Further, the step (2) specifically comprises the following steps:
(2-1) dispersing the first precursor material in a solvent, and enabling the first precursor material to be in full contact with the carbon source material in the solvent to form a uniform condensed mixture;
(2-2) carrying out spray drying, agglomeration granulation, freeze drying, extrusion granulation, wet granulation, melt granulation or fluidization granulation on the mixture to obtain secondary particles;
(2-3) carrying out heat treatment on the obtained secondary particles to obtain the final silicon-based particle/M-carbon @ carbon composite material.
Further, the solvent in step (2-1) includes one or more of water, sulfuric acid, liquid ammonia, carbon disulfide, hydrocarbons, hydrocarbon derivatives, alcohols, ethers, ketones, carboxylic acids, glycol derivatives, nitriles, amines, pyridine, and phenol in any ratio.
Furthermore, the dispersion mode in the step (2-1) comprises one or more of ultrasonic dispersion, stirring dispersion and ball milling dispersion, and the dispersion time is 10min-24 h.
Further, the solid-phase sintering in the step (3) is to directly carbonize the carbon source of the secondary particles under a certain sintering atmosphere and temperature system to obtain the carbon layer.
Furthermore, the sintering atmosphere is low pressure or purge gas, wherein the purge gas comprises one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton and xenon in any proportion, the gas flow is 1-1000sccm, and the sintering is completed under a vacuum low pressure state.
Further, the temperature system is as follows: the carbonization temperature is 200-1300 ℃, the heat preservation time is 0.5-100h, the temperature rising/reducing rate is 1-100 ℃/min, and the temperature rising/reducing rate is changed along with the reaction process.
Further, the carbon source adopted in the vapor deposition in the step (3) comprises methane, acetylene, propylene, toluene, benzene, deoiled asphalt or coal tar pitch; the carrier gas comprises one or more of hydrogen, nitrogen, argon, helium, neon, krypton and xenon in any proportion; the volume ratio of the carrier gas to the carbon source is 0.01-100, and the gas flow is 1-1000 sccm.
Further, the deposition temperature of the vapor deposition in the step (3) is 200-.
Compared with the prior art, the technical scheme of the application has the following beneficial effects or technical advantages:
the lithium ion battery cathode material is a silicon-based material with a core-shell structure, wherein a shell layer is a carbon material with good conductivity, and an inner core part is silicon-based particles modified by transition metal or compounds thereof. The coating of the carbon material improves the electronic conductance of the material as a whole. The transition metal can activate inert products (lithium oxide and lithium silicate) generated in the lithium intercalation process of the silicon-based material, and part of transition metal compounds can participate in reversible lithium deintercalation reaction, so that the coulomb efficiency of the material during lithium deintercalation is improved; and the silicon-based material is in a metal simple substance state under the potential of the silicon-intercalated and lithium-deintercalated, so that the current of the silicon-based material during lithium intercalation and deintercalation is homogenized in a state, the stress concentration caused by volume expansion is relieved, cracks are reduced, and the capacity attenuation of the material is delayed.
The technical key point of the invention is that the silicon-based particles modified by the transition metal or the compound thereof and the silicon-based uniformly distributed transition metal or the compound thereof are synthesized by a vapor deposition method or a wet chemical method, a physical mixing method and a solid-phase sintering method, and the silicon-based particles and the carbon are compounded to obtain the final high-performance silicon-based lithium ion battery cathode material.
The silicon-based negative electrode material of the lithium ion battery prepared by the invention has the advantages of high first coulombic efficiency, good rate capability, high lithium storage capacity, long cycle life and the like.
Drawings
FIG. 1 is a schematic structural diagram of a high-performance silicon-based lithium ion battery cathode material according to the present invention;
FIG. 2 is a flow chart of a preparation process of the high-performance silicon-based lithium ion battery cathode material;
fig. 3 is a charge-discharge curve of the negative electrode material of the silicon-based lithium ion battery prepared in an embodiment of the present invention;
fig. 4 is a scanning electron micrograph of the negative electrode material of the silicon-based lithium ion battery prepared in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
The invention discloses a high-performance silicon-based lithium ion battery cathode material and a preparation method thereof. The cathode material is of a core-shell structure, and the structural schematic diagram is shown in the attached figure 1: the inner core is silicon-based particles/M-carbon composite particles, M is transition metal or a compound thereof, and the coating layer is a carbon layer; the inner core is prepared by a method of firstly obtaining the silicon-based particle/M composite material by the silicon-based particles and the transition metal source, and then adding the carbon source for secondary granulation. The flow chart of the preparation process is shown in the attached figure 2, and the process can realize the industrial production of the lithium ion battery with excellent performances such as high specific capacity, long cycle life and the like.
[ example 1 ]
0.7g of nano silicon powder (Si,50nm) is weighed and evenly spread in an alumina crucible and is placed in a deposition position of a Chemical Vapor Deposition (CVD) furnace. Nickel cyclopentadienyl (Ni (C)5H5)2) As a metal source, 9.5g of the reaction gas was dissolved in xylene and placed in a gasifier at 175 ℃ slightly above the sublimation temperature of nickelocene. And (3) taking a hydrogen-argon mixed gas containing 5% of hydrogen as a carrier gas, introducing the carrier gas into a CVD furnace at a gas flow rate of 50sccm, heating to 500 ℃ at a heating rate of 5 ℃/min, preserving the temperature for 2h, cooling to room temperature at 5 ℃/min, and taking out a black sample Si-Ni.
Dispersing a sample Si-Ni and 1g of graphite (1 mu m) in a mass ratio of 1:2 in ethanol, carrying out ultrasonic treatment at a frequency of 20kHz for 20min, filling argon into a ball milling tank, carrying out ball milling for 2h in a planetary ball mill at a speed of 300r/min at normal temperature, and carrying out spray drying granulation to obtain Si-Ni/graphite composite particles.
Uniformly paving 1g of Si-Ni/graphite composite particles in an alumina crucible, placing the alumina crucible in a CVD furnace, introducing acetylene and argon gas in a volume ratio of 1:4 into the CVD furnace at a gas flow of 50sccm, heating to 600 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then stopping heating and cooling to room temperature to obtain the Si-Ni/graphite @ carbon composite material.
Weighing an active substance (Si-Ni/graphite @ carbon composite material), acetylene black and a binder according to a mass ratio of 70:15:15, uniformly mixing the active substance, the acetylene black and the binder with a proper amount of water to prepare slurry, uniformly coating the slurry on a copper foil, drying in vacuum, stamping to form a circular electrode piece, taking metal lithium as a counter electrode and 1mol/L LiPF6And EMC + DMC + EC (volume ratio of 1:1:1) is used as electrolyte, and Celgard 2400 is used as a diaphragm to form the button half cell.
And carrying out constant-current charge and discharge tests on the assembled battery, wherein the charge and discharge voltage range is 0.01-2.5V. The result shows that the first discharge specific capacity of the Si-Ni/graphite @ carbon composite material is only 940 mAh/g under the current density of 0.1A/g, the first coulombic efficiency is 92.1%, the specific capacity is 790mAh/g after circulation for 100 times, and the capacity is maintained to be 91%.
[ example 2 ]
Mixing silicon monoxide (SiO) and nano iron powder (50nm) in a mass ratio of 4:1, vacuum-sealing in a ball milling tank, and ball milling for 5 hours at normal temperature in a planetary ball mill at 300r/min to obtain a SiO-Fe sample.
Mixing SiO-Fe, carbon black (400nm) and Polyacrylonitrile (PAN) samples in a mass ratio of 1:1:2 in Dimethylformamide (DMF), carrying out ultrasonic treatment at a frequency of 20kHz for 20min, dispersing for 2h at a stirring speed of 800rpm, and carrying out high-pressure electrostatic spinning granulation to obtain the SiO-Fe/carbon black-PAN composite fiber.
Uniformly paving 1g of SiO-Fe/carbon black-PAN composite fiber in an alumina crucible, placing the alumina crucible in a tubular furnace, introducing argon-hydrogen mixed gas (with the gas flow of 50 sccm) containing 5% of hydrogen, heating to 600 ℃ at the heating rate of 10 ℃/min, preserving heat for 3h, and then cooling to room temperature at the temperature of 5 ℃/min to obtain the SiO-Fe/carbon black @ carbon composite material.
An electrode and a corresponding battery using the SiO-Fe/carbon black @ carbon composite as an active material were prepared in the same manner as in example 1.
The SiO-Fe/carbon black @ carbon composite material is corresponding to a battery and completes constant-current charge and discharge tests within the charge and discharge voltage range of 0.01-3V. The result shows that the first reversible specific capacity of the SiO-Fe/carbon black @ carbon composite material electrode is 1550mAh/g under the current density of 0.1A/g, the first coulombic efficiency is 79.1%, and the specific capacity is kept to be more than 85% of the initial capacity after 500 times of circulation.
[ example 3 ]
Ball-milling and crushing silicon monoxide (SiO) into submicron powder with the particle size of less than 200nm, mixing the submicron powder with cobalt chloride according to the mass ratio of 3:1, dissolving the submicron powder and the cobalt chloride in an aqueous solution containing 5% of sucrose, ultrasonically dispersing for 1h, magnetically stirring and dispersing for 2h, sealing the mixed solution into a rotary evaporation bottle, rotationally evaporating at 95rpm until the solvent disappears, taking out the mixed solution, drying in vacuum at 80 ℃ for 12h, grinding and crushing to 200 meshes, placing the mixed solution into a tube furnace, preserving heat at 700 ℃ for 3h, and then cooling to obtain a SiO-Co/C sample.
Uniformly paving 1g of SiO-Co/C sample in an alumina crucible, placing the alumina crucible in a CVD furnace, introducing acetylene and argon gas in a volume ratio of 1:5 into the CVD furnace at a gas flow rate of 100sccm, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and then stopping heating and cooling to room temperature to obtain the SiO-Co/C @ carbon composite material, wherein the shape of the SiO-Co/C @ carbon composite material is shown in figure 4.
An electrode having a SiO-Co/C @ carbon composite as an active material and a corresponding battery were prepared in the same manner as in example 1.
The SiO-Co/C @ carbon composite material is corresponding to a battery and completes constant current charging and discharging tests within the charging and discharging voltage range of 0.01-2V. The result shows that, as shown in figure 3, under the current density of 0.1A/g, the first reversible specific capacity of the SiO-Co/C @ carbon composite material electrode is 850mAh/g, the first coulombic efficiency is 75.12%, the specific capacity after 100 cycles is 782mAh/g, and the capacity is kept to 92%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The high-performance silicon-based lithium ion battery cathode material is characterized in that the cathode material is of a core-shell structure, the inner core of the cathode material is silicon-based particles/M-carbon composite particles, M is transition metal or a compound thereof, and the coating layer is a carbon layer; the inner core is prepared by a method of firstly obtaining the silicon-based particle/M composite material by the silicon-based particles and the transition metal source, and then adding the carbon source for secondary granulation.
2. The high-performance silicon-based lithium ion battery negative electrode material of claim 1, wherein the negative electrode material comprises the following elements in percentage by mass: si: 5 to 99 percent; c: 0.5-90%; transition metal: 0.01-30%; o: 0 to 55 percent; n: 0-15%, S: 0-15%, P: 0 to 15 percent.
3. The negative electrode material of the high-performance silicon-based lithium ion battery as claimed in claim 1 or 2, wherein the transition metal element comprises one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Cu, Ag, Au, and Pt; the existence form of M in the silicon-based particles/M-carbon composite particles comprises one or more of simple metal, metal-carbon alloy, metal-silicon alloy, metal nitride, metal oxide, metal phosphide, metal sulfide and metal silicate.
4. The preparation method of the high-performance silicon-based lithium ion battery negative electrode material according to claim 3, characterized by comprising the following steps:
(1) preparing a silicon-based particle/M composite material as a first precursor material by taking silicon-based particles and a transition metal source as raw materials;
(2) adding a carbon source material, uniformly mixing with the first precursor material, and obtaining silicon-based particles/M-carbon particles as a second precursor material by a secondary granulation method;
(3) and coating a uniform and continuous carbon layer on the surface of the second precursor material in a solid-phase sintering or vapor deposition mode to finally obtain the silicon-based particle/M-carbon @ carbon composite material.
5. The preparation method of the high-performance silicon-based lithium ion battery anode material according to claim 4, wherein the silicon-based particles in the step (1) comprise one or more of elemental silicon, a silicon-carbon composite material, a silicon oxide and a silicon oxide/carbon composite material; the average particle diameter of the first precursor material is 0.005-1 μm, and the specific surface area is 0.5-1000m2/g。
6. The method for preparing the high-performance silicon-based lithium ion battery anode material according to claim 4, wherein the first precursor material in the step (1) is prepared by any one method selected from a vapor deposition method, a wet chemical method, a physical mixing method and a solid-phase sintering method.
7. The method for preparing the high-performance silicon-based lithium ion battery anode material according to claim 4, wherein the carbon source material in the step (2) comprises one of saccharides, resins, rubbers, asphalt, polyvinylpyrrolidone, organic acids, polyethylene and derivatives thereof, polyalcohols, polyvinyl alcohol and derivatives thereof, or solid-phase carbon source materialsAny proportion combination of one or more; the solid-phase carbon source material comprises carbon fiber, graphite, graphene, carbon black, carbon nanoparticles, onion carbon, activated carbon or carbon nanotubes; the average grain diameter of the solid-phase carbon source material is 0.005-150 mu m, and the specific surface area is 0.05-1000m2(ii)/g; the mass ratio of the first precursor material to the carbon source material is 0.01-100.
8. The preparation method of the high-performance silicon-based lithium ion battery anode material according to claim 4, wherein the step (2) comprises the following steps:
(2-1) dispersing the first precursor material in a solvent, and enabling the first precursor material to be in full contact with the carbon source material in the solvent to form a uniform condensed mixture;
(2-2) carrying out spray drying, agglomeration granulation, freeze drying, extrusion granulation, wet granulation, melt granulation or fluidization granulation on the mixture to obtain secondary particles;
(2-3) carrying out heat treatment on the obtained secondary particles to obtain the final silicon-based particle/M-carbon @ carbon composite material.
9. The method for preparing the high-performance silicon-based lithium ion battery anode material according to claim 4, wherein the solid-phase sintering in the step (3) is to directly carbonize a carbon source of secondary particles under a certain sintering atmosphere and temperature system to obtain a carbon layer; the sintering atmosphere is low pressure or purging and ventilating, the purging gas comprises one or more of hydrogen, nitrogen, argon, helium, neon, oxygen, krypton and xenon in any proportion, and the gas flow is 1-1000 sccm; the temperature system is as follows: the carbonization temperature is 200-1300 ℃, the heat preservation time is 0.5-100h, the temperature rising/reducing rate is 1-100 ℃/min, and the temperature rising/reducing rate is changed along with the reaction process.
10. The method for preparing the high-performance silicon-based lithium ion battery anode material according to claim 4, wherein the carbon source adopted in the vapor deposition in the step (3) comprises methane, acetylene, propylene, toluene, benzene, deoiled asphalt or coal asphalt; the carrier gas comprises one or more of hydrogen, nitrogen, argon, helium, neon, krypton and xenon in any proportion; the volume ratio of the carrier gas to the carbon source is 0.01-100, and the gas flow is 1-1000 sccm; the deposition temperature of the vapor deposition is 200-1300 ℃, the deposition time is 0.5-100h, the temperature rising/reducing rate is 1-100 ℃/min, and the temperature rising/reducing rate is changed along with the reaction process.
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| CN113506861B (en) * | 2021-09-06 | 2022-05-17 | 北京壹金新能源科技有限公司 | Silicon-based composite negative electrode material of lithium ion battery and preparation method thereof |
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